Carbohydrate binders and materials made therewith

ABSTRACT

A binder comprising a polymeric binder comprising the products of a carbohydrate reactant and nucleophile is disclosed. The binder is useful for consolidating loosely assembled matter, such as fibers. Fibrous products comprising fibers in contact with a carbohydrate reactant and a nucleophile are also disclosed. The binder composition may be cured to yield a fibrous product comprising fibers bound by a cross-linked polymer. Further disclosed are methods for binding fibers with the carbohydrate reactant and polyamine based binder.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage entry under 35 USC §371(b) ofInternational Application No. PCT/EP2011/057364, filed May 7, 2011,which claims the benefit under 35 U.S.C. §119(e) of U.S. ProvisionalApplication Ser. No. 61/332,452, filed on May 7, 2010, the disclosuresof which are incorporated by reference in their entirety.

TECHNICAL FIELD

This disclosure relates to a binder formulation and materials madetherewith comprising a carbohydrate-based binder and a method forpreparing the same. In particular, a binder comprising the reactionproducts of a carbohydrate and a nucleophile and materials madetherewith is described.

BACKGROUND

Binders are useful in fabricating articles because they are capable ofconsolidating non- or loosely-assembled matter. For example, bindersenable two or more surfaces to become united. In particular, binders maybe used to produce products comprising consolidated fibers.Thermosetting binders may be characterized by being transformed intoinsoluble and infusible materials by means of either heat or catalyticaction. Examples of a thermosetting binder include a variety ofphenol-aldehyde, urea-aldehyde, melamine-aldehyde, and othercondensation-polymerization materials like furane and polyurethaneresins. Binder compositions containing phenol-aldehyde,resorcinol-aldehyde, phenol/aldehyde/urea, phenol/melamine/aldehyde, andthe like are used for the bonding of fibers, textiles, plastics,rubbers, and many other materials.

The mineral wool and fiber board industries have historically used aphenol formaldehyde binder to bind fibers. Phenol formaldehyde typebinders provide suitable properties to the final products; however,environmental considerations have motivated the development ofalternative binders. One such alternative binder is a carbohydrate basedbinder derived from reacting a carbohydrate and a multiprotic acid, forexample, U.S. Published Application No. 2007/0027283 and Published PCTApplication WO2009/019235. Another alternative binder is theesterification products of reacting a polycarboxylic acid and a polyol,for example, U.S. Published Application No. 2005/0202224. Because thesebinders do not utilize formaldehyde as a reagent, they have beencollectively referred to as formaldehyde-free binders.

One area of current development is to find a replacement for the phenolformaldehyde type binders across the entire range of products in thebuilding and automotive sector (e.g. fiberglass insulation, particleboards, office panels, and acoustical sound insulation). In particular,the previously developed formaldehyde-free binders may not possess allof the desired properties for all the products in this sector. Forexample, acrylic acid and poly(vinylalcohol) based binders have shownpromising performance characteristics. However, these are relativelymore expensive than phenol formaldehyde binders, are derived essentiallyfrom petroleum-based resources, and have a tendency to exhibit lowerreaction rates compared to the phenol formaldehyde based bindercompositions (requiring either prolonged cure times or increased curetemperatures). Carbohydrate-based binder compositions are made ofrelatively inexpensive precursors and are derived mainly from renewableresources; however, these binders may also require reaction conditionsfor curing that are substantially different from those conditions underwhich the traditional phenol formaldehyde binder system cured. As such,facile replacement of phenol formaldehyde type binders with an existingalternative has not been readily achievable.

SUMMARY

According to the present disclosure, a carbohydrate based binder isdescribed. The binder composition has properties that make it useful fora variety of applications; particularly, the binder may be used to bindloosely assembled matter such as fibers.

In illustrative embodiments, the present disclosure relates to a bindercomprising a polymeric product of a carbohydrate reactant and anucleophile. In one embodiment, the carbohydrate reactant is apolysaccharide. In one embodiment, the carbohydrate reactant is amonosaccharide or a disaccharide. In another embodiment, thecarbohydrate is a monosaccharide in its aldose or ketose form. Inanother embodiment, the carbohydrate reactant is selected from the groupconsisting of dextrose, xylose, fructose, dihydroxyacetone, and mixturesthereof. In another embodiment, the polymeric product is a thermosetpolymeric product.

In illustrative embodiments, the nucleophile is a di-functional. Inanother embodiment, the nucleophile is R₁-Q-R₂, wherein Q is alkyl,cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which isoptionally substituted having a nucleophilic moiety and a stabilizationmoiety, R₁ is selected from the group consisting of an amine, an azide,a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, ahalogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and analkoxide, and R₂ is selected from the group consisting of an amine, anamide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate,a phosphono, a hydroxyl, a hydrogen, a sulphono, a sulpho, a sulfinyl,and a sulfhydryl (thiol). In one embodiment, the nucleophile includes anamine functional group.

In illustrative embodiments, the mole ratio of the carbohydrate reactantto the nucleophile is in the range of about 1:1 to about 30:1. Inanother embodiment, the mole ratio of the carbohydrate reactant to thenucleophile is in the range of about 2:1 to about 10:1. In anotherembodiment, an aqueous extract of the polymeric product has a pH in therange of about 5 to about 9. In another embodiment, an aqueous extractof the polymeric product is essentially colorless. In yet anotherembodiment, the polymeric product is phenol-free and/orformaldehyde-free. In another embodiment, an aqueous extract of thepolymeric product is capable of reducing Benedict's reagent. In anotherembodiment, the polymeric product absorbs light between 400 and 500 nm,for example, in one embodiment, at 420 nm.

In an illustrative embodiment, a method of making a collection of matterbound with a polymeric binder comprises preparing a solution containingreactants for producing the polymeric binder and a solvent, wherein thereactants include a carbohydrate reactant and a nucleophile; disposingthe solution onto the collection of matter; volatilizing the solvent toform an uncured product, and subjecting the uncured product toconditions that cause the carbohydrate reactant and the nucleophile topolymerize to form the polymeric binder. In one embodiment, thecollection of matter comprises fibers selected from the group consistingof mineral fibers (slag wool fibers, rock wool fibers, or glass fibers),aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimidefibers, polyester fibers, rayon fibers, and cellulosic fibers. Inanother embodiment, the collection of matter comprises particulates suchas coal or sand. In another embodiment, the collection of matter isglass fibers. In yet another embodiment, the glass fibers are present inthe range from about 70% to about 99% by weight. In another embodiment,the collection of matter comprises cellulosic fibers. For example, thecellulosic fibers may be wood shavings, sawdust, wood pulp, or groundwood. In yet another embodiment, the cellulosic fibers may be othernatural fibers such as jute, flax, hemp, or straw.

In illustrative embodiments, the method of making a collection of matterbound with a polymeric binder further includes preparing a solution byadding an amount of a carbohydrate reactant and an amount of anucleophile so that the molar ratio is in the range of about 2:1 toabout 10:1, respectively. In one embodiment, preparing the solutionincludes adding the carbohydrate reactant and the nucleophile to anaqueous solution. In another embodiment, preparing the solution includesadjusting the pH of the solution to within the range of about 8 to about13, for example, in one embodiment, the range of about 8 to about 12.

In illustrative embodiments, the present disclosure relates to acomposition comprising a collection of matter and a binder; the bindercomprising the polymeric products of a reaction between a carbohydratereactant and a nucleophile, the polymeric products being substantiallywater insoluble. In one embodiment, the collection of matter includesmineral fibers (slag wool fibers, rock wool fibers, or glass fibers),aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimidefibers, polyester fibers, rayon fibers, and cellulosic fibers. Forexample, cellulosic fibers include wood shavings, sawdust, wood pulp,and/or ground wood. In one embodiment, the carbohydrate reactant isselected from the group consisting of dextrose, xylose, fructose,dihydroxyacetone, and mixtures thereof. In another embodiment, thenucleophile is selected from the group consisting of a diamine,triamine, tetramine, and pentamine. In one embodiment, the nucleophileis R₁-Q-R₂, wherein Q is alkyl, cycloalkyl, heteroalkyl, orcycloheteroalkyl, each of which is optionally substituted, R₁ is anucleophilic moiety, and R₂ is a stabilization moiety. In oneembodiment, R₁ is selected from the group consisting of an amine, anazide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, ahalogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and analkoxide. In another embodiment, R₂ is selected from the groupconsisting of an amine, an amide, an imine, an imide, a nitro, anitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, asulphono, a sulpho, a sulfinyl, and a sulfhydryl (thiol).

In another embodiment, the composition further comprises asilicon-containing compound. In one embodiment the silicon-containingcompound is a functionalized silylether or a functionalizedalkylsilylether, such as for example, an amino-functionalizedalkylsilylether. For example, in one embodiment, the silicon-containingcompound may be gamma-aminopropyltriethoxysilane,gamma-glycidoxypropyltrimethoxysilane, oraminoethylaminopropyltrimethoxysilane, or a mixture thereof. In anotherembodiment, the silicon-containing compound may be an aminofunctionaloligomeric siloxane. In another embodiment, the composition comprises acorrosion inhibitor selected from the group consisting of dedusting oil,monoammonium phosphate, sodium metasilicate pentahydrate, melamine,tin(II) oxalate, and a methylhydrogen silicone fluid emulsion.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic of a Maillard reaction, which culminates in theproduction of melanoidins.

FIG. 2 shows a schematic of a representative Amadori rearrangement.

FIG. 3 shows the cure temperature profile (Y-axis in ° C.) of the centerof a fiberglass mat sample for different binders during a heat moldingcycle (X-axis in minutes of mold time) using a mold press with atemperature controlled platen at 204° C. Binder 1 (♦) is a phenolformaldehyde binder (Comparative Example 2); Binder 2 (▪) is acarbohydrate—inorganic acid binder (Comparative Example 3); and Binder 3(X) is a dextrose—ammonia—hexamethylene diamine (HMDA) binder (Example5).

DETAILED DESCRIPTION

While the invention is susceptible to various modifications andalternative forms, specific embodiments will herein be described indetail. It should be understood, however, that there is no intent tolimit the invention to the particular forms described, but on thecontrary, the intention is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the invention.

The present disclosure relates to a binder composition having unexpectedutility in consolidating non- or loosely-assembled matter. The bindercomposition represents an unexpected advancement in the current state oftechnology in the area of binder compositions. Specifically, the binderoffers improvements in performance and provides for more simplified andadvantageous manufacturing methodologies, while maintaining theenvironmentally sound advantages that are characteristic of acarbohydrate based binder system.

As used herein, the term binder solution is the solution of chemicalswhich can be substantially dehydrated to form an uncured binder. As usedherein, the binder or binder composition may be cured, uncured, orpartially cured. The composition of the uncured binder is referred to asan uncured binder composition. An uncured binder is a substantiallydehydrated mixture of chemicals which can be cured to form a curedbinder. Substantially dehydrated means that the solvent (typically wateror a mixture thereof) used to make the binder solution is vaporized tothe extent that the viscosity of the remaining material (comprising thebinder reactants and solvent) is sufficiently high to create cohesionbetween the loosely assembled matter; thus, the remaining material is anuncured binder. In one embodiment, the solvent is less than 65% of thetotal weight of the remaining material. In another embodiment, asubstantially dehydrated binder has a moisture content between about 5%and about 65% water by weight of total binder. In another embodiment,the solvent may be less than 50% of the total weight of the remainingmaterial. In yet another embodiment, the solvent may be less than 35% ofthe total weight of the remaining material. In another embodiment, asubstantially dehydrated binder has between about 10% and about 35%water by weight of total binder. In another embodiment, the solvent maycomprise less than about 20% of the total weight of the remainingmaterial.

In illustrative embodiments, an uncured binder may be colorless, white,off white, ochre or yellow to brownish sticky substance that is, atleast partially, water soluble. As used herein, the term cured binderdescribes the polymeric product of curing the uncured bindercomposition. The cured binder may have a characteristic brown to blackcolor. While described as brown or black, another characteristic is thatthe binder tends to absorb light over a broad range of wavelengths. Inparticular, there may be higher absorbance at approximately 420 nm. Asthe polymer is extensively cross-linked, the cured binder issubstantially insoluble. For example, the binder is predominantlyinsoluble in water. As described herein, the uncured binder providessufficient binding capacity to consolidate fibers; however, the curedbinder imparts the robust, long-lasting durability and physicalproperties commonly associated with cross-linked polymers.

In illustrative embodiments, the binder reactants described herein aresoluble in water and the binder solution is a solution of the binderreactants in an aqueous solution. In one embodiment, a surfactant isincluded in the aqueous solution to increase the solubility ordispersability of one or more binder reactants or additives. Forexample, a surfactant may be added to the aqueous binder solution toenhance the dispersibility of a particulate additive. In one embodiment,a surfactant is used to create an emulsion with a non-polar additive orbinder reactant. In another embodiment, the binder solution comprisesabout 0.01% to about 5% surfactant by weight based on the weight of thebinder solution.

In illustrative embodiments, the binder solutions described herein canbe applied to mineral fibers (e.g., sprayed onto the mat or sprayed ontothe fibers as they enter the forming region), during production ofmineral fiber insulation products. Once the binder solution is incontact with the mineral fibers the residual heat from the mineralfibers (note that the glass fibers, for example, are made from moltenglass and thus contain residual heat) and the flow of air through and/oraround the product will cause a portion of the water to evaporate fromthe binder solution. Removing the water leaves the remaining componentsof the binder on the fibers as a coating of viscous or semi-viscoushigh-solids mixture. This coating of viscous or semi-viscous high-solidsmixture functions as a binder. At this point, the mat has not beencured. In other words, the uncured binder functions to bind the fibersin the mat.

Furthermore, it should be understood that the above described uncuredbinders can be cured. For example, the process of manufacturing a curedinsulation product may include a subsequent step in which heat isapplied as to cause a chemical reaction in the uncured bindercomposition. For example, in the case of making fiberglass insulationproducts, after the binder solution has been applied to the fibers anddehydrated, the uncured insulation product may be transferred to acuring oven. In the curing oven the uncured insulation product is heated(e.g., from about 300° F. to about 600° F. [from about 150° C. to about320° C.]), causing the binder to cure. The cured binder is aformaldehyde-free, water-resistant binder that binds the glass fibers ofthe insulation product together. Note that the drying and thermal curingmay occur either sequentially, simultaneously, contemporaneously, orconcurrently.

In illustrative embodiments, an uncured fiber product comprises about 3%to about 40% of dry binder solids (total uncured solids by weight). Inone embodiment, the uncured fiber product comprises about 5% to about25% of dry binder solids. In another embodiment, the uncured fiberproduct comprises about 50% to about 97% fibers by weight.

As mentioned herein with respect to a binder on mineral fibers, a curedbinder is the product of curing binder reactants. The term curedindicates that the binder has been exposed to conditions so as toinitiate a chemical change. Examples of these chemical changes include,but are not limited to, (i) covalent bonding, (ii) hydrogen bonding ofbinder components, and (iii) chemically cross-linking the polymersand/or oligomers in the binder. These changes may increase the binder'sdurability and solvent resistance as compared to the uncured binder.Curing a binder may result in the formation of a thermoset material. Inaddition, a cured binder may result in an increase in adhesion betweenthe matter in a collection as compared to an uncured binder. Curing canbe initiated by, for example, heat, microwave radiation, and/orconditions that initiate one or more of the chemical changes mentionedabove. While not limited to a particular theory, curing may include thereaction of the carbohydrate and the nucleophile in a nucleophilicaddition reaction or nucleophilic addition-elimination reaction.

In a situation where the chemical change in the binder results in therelease of water, e.g., polymerization and cross-linking, a cure can bedetermined by the amount of water released above that which would occurfrom drying alone. The techniques used to measure the amount of waterreleased during drying as compared to when a binder is cured, are wellknown in the art.

In illustrative embodiment, the nucleophile is a nitrogen containingcompound. In one embodiment, the cured binder composition comprises anitrogenous polymer. In one embodiment, the nitrogenous polymer is brownto black in color. While not limited to a particular theory, the curedbinder composition comprises a mixture of high molecular weightpolymers. The high molecular weight polymers may be characterized asbeing highly cross-linked. Furthermore, the high molecular weightpolymers may be characterized as being brown, complex, furanring-containing and nitrogen-containing polymers. High molecular weight,as used herein, includes those polymers having a molecular weight inexcess of 100,000 Daltons. Being comprised of highly cross-linkedpolymeric chains, the molecular weight of the high molecular weightpolymers described herein approaches infinity. Accordingly, themolecular weight of the high molecular weight polymers may be a functionof the mass and physical dimensions of the polymer being analyzed. Forexample, a unitary sample of melanoidins having a mass of 3 grams may bepresumed to comprise a single polymeric molecule due to the extensivecross-linking. Accordingly, the molecular weight of the polymer would beapproximately 1.8×10²⁴ grams per mole (being the product of the samplemass and Avogadro's number). As used herein, a high molecular weightpolymer includes polymers with a molecular weight in the order ofbetween about 1×10⁵ and about 1×10²⁴ grams per mole.

While not be limited to a particular theory, it is understood that highmolecular weight polymers vary in structure according to the reactantsand conditions of preparation. It is also known that high molecularweight polymers possess a carbon to nitrogen ratio which increases withtemperature and time of heating. Furthermore, high molecular weightpolymers possess saturated, unsaturated and aromatic character. In oneembodiment, the high molecular weight polymers possessed a degree ofunsaturation and aromaticity that increased with temperature (curetemperature) and time of heating (cure time). The high molecular weightpolymers also contained the C-1 of those sugars incorporated asreactants in a variety of structures within the polymer. The highmolecular weight polymers may also contain carbonyl, carboxyl, amine,amide, pyrrole, indole, azomethine, ester, anhydride, ether, methyland/or hydroxyl groups. Depending on the complexity of the structure,infrared spectroscopy may be useful in the identification of one or moreof these functional groups. While not so classified here, one ofordinary skill would appreciate that the binder may be classifiableaccording to the existence of a particular bond present such as apolyester, polyether, polyamide, etc.

Another manner in which the binder is characterizable is throughanalysis of the gaseous compounds produced during pyrolysis of the curedbinder. Gas pyrolysis of a cured binder within the scope of the presentdisclosure may yield approximately 0.5 to about 15% (by relative peakarea) of one or more of the following compounds: 2-cyclopenten-1-one,2,5-dimethyl-furan, furan, 3-methyl-2,5-furandione, phenol,2,3-dimethyl-2-cyclopenten-1-one, 2-methyl phenol, 4-methyl phenol,2,4-dimethyl-phenol, dimethylphthalate, octadecanoic acid, orerucylamide. Fingerprinting in pyrolysis gas chromatography massspectrometry (Py GC-MS) carried out at 770° C. of a binder sampleprepared using hexamethylenediamine as the polyamine component showspyridine and a number of components which are pyrrole or pyridinederivatives (a methylpyridine, a methylpyrrole, dimethylpyridines, adimethylpyrrole, an ethyl methylpyrrole, and other pyrrole relatedN-containing components). Another manner in which the binder may beidentified is whether a solution containing the binder (or an extractsolution) is capable of reducing Benedict's reagent. In one embodiment,a solution in contact with the binder or an aqueous extract thereofreduces Benedict's reagent.

One aspect of the present disclosure is that the binders describedherein are environmentally friendly. Parallel to advancing governmentregulation, the present disclosure describes a binder that may be madeformaldehyde-free. Additionally, the chemistry described herein isessentially free of formaldehyde and phenol. In this sense, neitherformaldehyde nor phenol is used as a reagent within the scope of thepresent disclosure. While both may be added to obtain a binder withpotentially useful properties, one aspect of the present disclosure is abinder that can be made free from both of these reactants. In anotheraspect, the present binder composition may be manufactured without theuse of volatile reactants. In one embodiment, the nucleophile and thecarbohydrate are both non-volatile reactants. As used herein, a volatilereactant is one that has a vapor pressure greater than 10 kPa at 20° C.Similarly, as used herein, a non-volatile reactant has a vapor pressureof less than about 10 kPa at 20° C. Specifically and as an example, thepresent binder may be manufactured without the addition of ammonia or anammonia releasing compound. In one embodiment, the nucleophile has avapor pressure of less than about 0.5 kPa at 60° C.

Another environmentally friendly aspect of the present disclosure isthat the primary reactants of the binder are carbohydrates.Carbohydrates are considered a renewable resource. However, the currentstate of the art primarily uses petroleum-derived reactants for themanufacture of binder compositions. In another aspect, the binder ismade through chemical reactions which can occur at lower temperaturesthan those comparable systems described in the prior art. As such, thecuring ovens and manufacturing equipment can be operated at lowertemperatures, saving valuable resources. In the alternative and in arelated manner, the binder described herein cures more quickly thancomparable binders currently used when subjected to similar curingtemperatures. Accordingly, through either approach, one aspect of thepresent disclosure is that the carbon footprint of a formed productusing the presently disclosed binder may be substantially reducedcompared to a comparable binder made according to the current state ofthe art, for example a phenol formaldehyde based product.

In addition to the environmental benefits, the present bindercomposition and materials made therewith can be made having performancecharacteristics equivalent or exceeding those of comparable bindersystems, for example, phenol formaldehyde binders. In one aspect, abinder according to the present disclosure provides articles madetherewith sufficient tensile strength to allow for die-cutting,fabrication, lamination, and installation in OEM applications. In oneaspect, a binder according to the present disclosure has water hold-up(weatherability) comparable to that of a phenol formaldehyde binder.Other performance characteristic that may be relevant for a particularapplication include product emissions, density, loss on ignition,thickness recovery, dust, tensile strength, parting strength, durabilityof parting strength, bond strength, water absorption, hot surfaceperformance, corrosivity on steel, flexural rigidity,stiffness-rigidity, compressive resistance, conditioned compressiveresistance, compressive modulus, conditioned compressive modulus, andsmoke development on ignition. One aspect of the present disclosure isthat the extract of the cured binder is essentially pH neutral, forexample between a pH of 6 and 8. Another aspect of the presentdisclosure is that the present binder enables the manufacture ofproducts having comparable relevant performance characteristics tophenol formaldehyde binder compositions.

Illustratively, in one embodiment, a binder according to the presentdisclosure invention has the advantage of yielding essentially colorlessaqueous extracts. This feature of the present disclosure makes thebinder desirable in applications such as ceiling tiles, furniture, oroffice panels, wherein the finished product may come into contact withwater. A cured manufactured good made with the present binder shows anexcellent resistance to discoloration or bleeding after coming incontact with moisture or water. Furthermore, in such an embodiment, thewater that contacts the binder does not leave a residual color on otherarticles or parts which it may contact subsequent to contact the binder.For example, in one embodiment, the binder may be used to bind glassfibers in an office panel application. Covering the bound fiberglasscomposition may be a light colored fabric. Advantageously, in oneembodiment, water contacting the fiberglass composition does not leave acolored residue upon the fabric after the office panel has dried.

In addition to the performance characteristics, the manufacturingprocesses and methods involving the presently disclosed binder have anumber of unexpected advantages over previously described binders. Inone aspect, as previously described with respect to the environmentalbenefits, the present binder may be manufactured without the use ofhighly volatile reactants. Accordingly, manufacturing emission controlsare under a reduced burden. Furthermore, the reaction efficiency ishigher because reactant loss due to vaporization is reduced.Accordingly, one aspect of the present disclosure is that the compoundsused herein are substantially non-volatile, thus the steps one must taketo mitigate undesirable emissions are reduced.

According to another aspect, the reactants that react to form a binderare sufficiently slow to react such that a one step/one pot bindersystem can be used. According to this aspect, the reactant compounds aresufficiently slow to react that they can be added to a single reactantsolution and stored for a reasonable amount of time during which theycan be applied to a product using one distribution system. Thiscontrasts with those binder systems which react at low temperaturesresulting in insoluble reaction products within binder solution deliverysystems. As used here, a reasonable amount of time for storage withoutsubstantial (>5%) polymeric precipitation is two weeks.

Another aspect of the present disclosure is that, although the binder issufficiently unreactive at room temperature conditions to facilitate aone-pot approach, it is sufficiently reactive at elevated temperaturesto cure at very low temperatures and/or very short curing residencytimes. In one respect, the lowered curing temperature reduces the riskof an insulation product undergoing flameless combustion and/or causingline fires. As used here, very low temperatures are characterized asless than or equal to about 120° C. As used here, very short cure timesare less than or equal to about 4 min.

In illustrative embodiments, the binder composition includes an acid oran acid salt to increase the shelf life of the uncured binder or bindersolution. While this acid is not a reactant or a catalyst, it may beincluded to slow or inhibit the binder reactants from forming the binderwhile the binder solution or uncured binder is being maintained understorage conditions. For example, a volatile acid or acid salt may beincluded in the binder solution or uncured binder that slows or inhibitsthe curing reaction at ambient conditions. However, the acid may beremoved by heating the binder solution or uncured binder so that theacid is volatilized and the pH of the binder solution or uncured binderincreases. In one embodiment, the binder composition includes ashelf-life extending acid. In another embodiment, the binder compositionincludes a mole ratio of shelf-life extending acid to nucleophile ofabout 1:20 to about 1:1.

Another aspect of the present disclosure is a binder having a cure rate,cycle time, and cure temperature which meets or exceeds those cure ratesthat a comparable phenol and formaldehyde type binder may exhibit withinthe scope of a comparable use. In this respect, the present binder canbe used as a direct replacement to phenol formaldehyde resins inapplications without modification to the equipment. Furthermore, thepresent binder enables the modification of the curing temperature andtimes so that both the reaction temperatures and cure times may bereduced. This reduction has the effect of reducing the energyconsumption of the process overall and reduces the environmental impactof manufacturing the product. Furthermore, the lower cure temperatureshave the further effect of increasing the safety of manufacturingprocess. Another effect of the lower cure temperatures is a reduction inthe risk of flameless combustion or fire.

In the manufacture of insulation products, the heat released by theexothermic curing reaction may result in self-heating of the product.Self-heating is typically not problematic so long as the heat dissipatesfrom the product. However, if the heat increases the temperature of theproduct to the point where oxidative processes commence, theself-heating may cause significant damage to the product. For example,flameless combustion or oxidation may occur when the temperature of theinsulation product exceeds about 425° F. (210° C.). At thesetemperatures, the exothermic combustion or oxidation processes promotefurther self-heating and the binder may be destroyed. Furthermore, thetemperature may increase to a level in which fusing or devitrificationof the glass fibers is possible. Not only does this damage the structureand value of the insulation product, it may also create a fire hazard.

Another aspect of the present disclosure is that the binder system isessentially non-corrosive with or without the addition of corrosioninhibitors. Furthermore, the binder system does not require the additionof any organic or inorganic acid or salts thereof as catalyst or activeingredient. Accordingly, one aspect of the present binder is that it maybe made essentially acid-free. Furthermore, the binder may bemanufactured under entirely alkaline conditions. As used here, the termacid includes those compounds which are characterizable primarily fortheir acidic character such multiprotic inorganic and organic acids(e.g. sulfuric acid and citric acid). This aspect reduces the wear andmaintenance requirements of the manufacturing equipment and enhancesworker safety.

In illustrative embodiments, a binder comprises a polymeric product of acarbohydrate reactant and a nucleophile. As used herein, the termcarbohydrate reactant refers to a monosaccharide, a disaccharide, apolysaccharide, or a reaction product thereof. In one embodiment, thecarbohydrate reactant may be a reducing sugar. As used herein, reducingsugar indicates one or more sugars that contain aldehyde groups, or thatcan isomerize, i.e., tautomerize, to contain aldehyde groups, whichgroups may be oxidized with, for example, Cu⁺² to afford carboxylicacids. It is also appreciated that any such carbohydrate reactant may beoptionally substituted, such as with hydroxy, halo, alkyl, alkoxy, andthe like. It is further appreciated that in any such carbohydratereactant, one or more chiral centers are present, and that both possibleoptical isomers at each chiral center are contemplated to be included inthe invention described herein. Further, it is also to be understoodthat various mixtures, including racemic mixtures, or otherdiastereomeric mixtures of the various optical isomers of any suchcarbohydrate reactant, as well as various geometric isomers thereof, maybe used in one or more embodiments described herein. While non-reducingsugars, for instance sucrose, may not be preferable, they maynone-the-less be useful within the scope of the present disclosure byin-situ conversion to a reducing sugar (i.e. conversion of sucrose toinvert sugar is a method known in the art). Further, it is alsounderstood that a monosaccharide, a disaccharide, or polysaccharide maybe partially reacted with a precursor to form a carbohydrate reactionproduct. To the extent that the carbohydrate reaction product is derivedfrom a monosaccharide, a disaccharide, or a polysaccharide and maintainssimilar reactivity with the nucleophile to form reaction productssimilar to those of a monosaccharide, a disaccharide, or apolysaccharide with a nucleophile, the carbohydrate reaction product iswithin the scope of term carbohydrate reactant.

In one aspect, any carbohydrate reactant should be sufficientlynonvolatile to maximize its ability to remain available for reactionwith the nucleophile. The carbohydrate reactant may be a monosaccharidein its aldose or ketose form, including a triose, a tetrose, a pentose,a hexose, or a heptose; or a polysaccharide; or combinations thereof.For example, when a triose serves as the carbohydrate reactant, or isused in combination with other reducing sugars and/or a polysaccharide,an aldotriose sugar or a ketotriose sugar may be utilized, such asglyceraldehyde and dihydroxyacetone, respectively. When a tetrose servesas the carbohydrate reactant, or is used in combination with otherreducing sugars and/or a polysaccharide, aldotetrose sugars, such aserythrose and threose; and ketotetrose sugars, such as erythrulose, maybe utilized. When a pentose serves as the carbohydrate reactant, or isused in combination with other reducing sugars and/or a polysaccharide,aldopentose sugars, such as ribose, arabinose, xylose, and lyxose; andketopentose sugars, such as ribulose, arabulose, xylulose, and lyxulose,may be utilized. When a hexose serves as the carbohydrate reactant, oris used in combination with other reducing sugars and/or apolysaccharide, aldohexose sugars, such as glucose (i.e., dextrose),mannose, galactose, allose, altrose, talose, gulose, and idose; andketohexose sugars, such as fructose, psicose, sorbose and tagatose, maybe utilized. When a heptose serves as the carbohydrate reactant, or isused in combination with other reducing sugars and/or a polysaccharide,a ketoheptose sugar such as sedoheptulose may be utilized. Otherstereoisomers of such carbohydrate reactants not known to occurnaturally are also contemplated to be useful in preparing the bindercompositions as described herein. In one embodiment, the carbohydratereactant is high fructose corn syrup.

In illustrative embodiments, the carbohydrate reactant is apolysaccharide. In one embodiment, the carbohydrate reactant is apolysaccharide with a low degree of polymerization. In one embodiment,the polysaccharide is molasses, starch, cellulose hydrolysates, ormixtures thereof. In one embodiment, the carbohydrate reactant is astarch hydrolysate, a maltodextrin, or a mixture thereof. Whilecarbohydrates of higher degrees of polymerization may not be preferable,they may none-the-less be useful within the scope of the presentdisclosure by in-situ depolymerization (i.e. depolymerization throughammoniation at elevated temperatures is a method known in the art).

Furthermore, the carbohydrate reactant may be used in combination with anon-carbohydrate polyhydroxy reactant. Examples of non-carbohydratepolyhydroxy reactants which can be used in combination with thecarbohydrate reactant include, but are not limited to,trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol,partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinylacetate, and mixtures thereof. In one aspect, the non-carbohydratepolyhydroxy reactant is sufficiently nonvolatile to maximize its abilityto remain available for reaction with a monomeric or polymericpolyamine. It is appreciated that the hydrophobicity of thenon-carbohydrate polyhydroxy reactant may be a factor in determining thephysical properties of a binder prepared as described herein.

As used herein, a nucleophile is a reagent that forms a bond to itsreaction partner (the electrophile) by donating both bonding electrons.As used herein, an electrophile is a reagent that forms a bond to itsreaction partner (the nucleophile) by accepting both bonding electronsfrom that reaction partner. Illustratively, the electrophile is thecarbohydrate described herein. Specifically, the electrophilic group isthe carbon associated with the aldose or ketose form of thecarbohydrate. For example, C-1 of glucose is electropositive due to thealdose functionality and reacts with a nucleophile of the presentdisclosure. In another example, C-2 of fructose is electropositive dueto the ketose functionality and reacts with a nucleophile of the presentdisclosure. While described as an electrophile in its initialinteraction with the nucleophile, one skilled in the art will appreciatethat the carbohydrate is not limited to acting only as an electrophilewithin the scope of reactions which may occur. For example, the hydroxylgroups of the carbohydrate may act as a nucleophile depending on thepresence of a reactive nucleophile. Furthermore, while the initialreaction between the nucleophile and the carbohydrate may correctlyclassify the carbohydrate as an electrophile, the product of thatreaction may exhibit both nucleophilic and electrophilic functionalityin further reactions.

In illustrative embodiments, the nucleophile is sufficientlynucleophilic to react with a carbohydrate in its aldose or ketose formin a solution having a pH as described herein and at a temperaturedescribed herein. In one embodiment, the nucleophile includes a cationicstabilization moiety. As used herein, a cationic stabilization moiety isa chemical group on the nucleophile which stabilizes the cation thatforms upon the nucleophilic attack. For example, one nucleophile withinthe scope of the present disclosure is a diamine. Upon nucleophilicattack of a carbonyl by a primary amine, a cation of a Schiff base isformed. While the diamine's first amine acts in the role of anucleophile, the second amine acts in the role of a cationicstabilization moiety as it stabilizes the cation of the Schiff base.Further rearrangement of the cation of the Schiff base to the enol orketo form is known to proceed spontaneously. The cation that forms uponnucleophilic attack is similarly stabilized (as a Schiff base is) by thestructure of the nucleophile. In another aspect, the structure of thenucleophile accelerates rearrangement by stabilizing the positive chargethat is acquired while the compound is in the form of a cation thatformed upon nucleophilic attack.

It was discovered that this spontaneous reaction is further facilitatedby dehydration, as the rate was increased in dehydrated samples. It isbelieved that the importance of the stabilization moiety has not beendiscussed in the prior art within the scope of the present applicationas the enhanced effect of using a nucleophile of the present disclosurehas not previously been disclosed. Accordingly, one aspect of thepresent disclosure is that the nucleophile is of a type that providesstability to a cation of a nucleophilic base during a subsequentrearrangement. In another aspect, the nucleophile is of a type thatprovides stability to a cation of a nucleophilic base during asubsequent rearrangement while in a substantially dry state.

In illustrative embodiments, the nucleophile is R₁-Q-R₂, wherein Q isalkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which isoptionally substituted, R₁ is a nucleophilic moiety, and R₂ is thestabilization moiety. In one embodiment, R₁ is selected from the groupconsisting of an amine, an azide, a cyanate, an isocyanate, a thiol, adisulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, acarboxylate, a hydroxyl, and an alkoxide. In another embodiment, R₂ isselected from the group consisting of an amine, an amide, an imine, animide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, ahydroxyl, a hydrogen, a sulphono, a sulpho, a sulfinyl, and a sulfhydryl(thiol).

In one embodiment, the nucleophile is a primary amine. As used herein, aprimary amine is an organic compound having one or more primary aminegroups. Within the scope of the term primary amine are those compoundswhich can be modified in situ or isomerize to generate a compound havingone or more primary amine groups. In one embodiment, the primary aminemay be a molecule having the formula of H₂N-Q-R, wherein Q is an alkyl,cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which may beoptionally substituted and R includes a cationic stabilization moietyselected from the group consisting of an amine, an amide, an imine, animide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, ahydroxyl, a hydrogen, a sulphono, a sulpho, a sulfinyl, and a sulfhydryl(thiol).

In one embodiment, Q is an alkyl selected from the group consisting ofC₂-C₂₄. In another embodiment, Q is an alkyl selected from the groupconsisting of C₂-C₈. In another embodiment, Q is an alkyl selected fromthe group consisting of C₃-C₇. In yet another embodiment, Q is a C₆alkyl. In one embodiment, Q is selected from the group consisting of acyclohexyl, cyclopentyl or cyclobutyl. In another embodiment, Q is abenzyl. In one embodiment, R₁-Q-R₂ is 2-[(2-aminoethyl)amino]ethanol. Inanother embodiment of R₁-Q-R₂, each of R₁ and R₂ is thiol.

In one embodiment, R₁ is an amine. In a further embodiment of the above,R₂ is an amine, an amide, an imine, or an imide. In a further embodimentof the above, R₂ is an amine.

As used herein, the term “alkyl” includes a chain of carbon atoms, whichis optionally branched. As used herein, the term “alkenyl” and “alkynyl”includes a chain of carbon atoms, which is optionally branched, andincludes at least one double bond or triple bond, respectively. It is tobe understood that alkynyl may also include one or more double bonds. Itis to be further understood that alkyl is advantageously of limitedlength, including C₁-C₂₄, C₁-C₁₂, C₁-C₈, C₁-C₆, and C₁-C₄. It is to befurther understood that alkenyl and/or alkynyl may each beadvantageously of limited length, including C₂-C₂₄, C₂-C₁₂, C₂-C₈,C₂-C₆, and C₂-C₄. It is appreciated herein that shorter alkyl, alkenyl,and/or alkynyl groups may add less hydrophilicity to the compound andaccordingly will have different reactivity towards the carbohydratereactant and solubility in a binder solution.

As used herein, the term “cycloalkyl” includes a chain of carbon atoms,which is optionally branched, where at least a portion of the chain incyclic. It is to be understood that cycloalkylalkyl is a subset ofcycloalkyl. It is to be understood that cycloalkyl may be polycyclic.Illustrative cycloalkyl include, but are not limited to, cyclopropyl,cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyleth-2-yl,adamantyl, and the like. As used herein, the term “cycloalkenyl”includes a chain of carbon atoms, which is optionally branched, andincludes at least one double bond, where at least a portion of the chainin cyclic. It is to be understood that the one or more double bonds maybe in the cyclic portion of cycloalkenyl and/or the non-cyclic portionof cycloalkenyl. It is to be understood that cycloalkenylalkyl andcycloalkylalkenyl are each subsets of cycloalkenyl. It is to beunderstood that cycloalkyl may be polycyclic. Illustrative cycloalkenylinclude, but are not limited to, cyclopentenyl, cyclohexylethen-2-yl,cycloheptenylpropenyl, and the like. It is to be further understood thatchain forming cycloalkyl and/or cycloalkenyl is advantageously oflimited length, including C₃-C₂₄, C₃-C₁₂, C₃-C₈, C₃-C₆, and C₅-C₆. It isappreciated herein that shorter alkyl and/or alkenyl chains formingcycloalkyl and/or cycloalkenyl, respectively, may add less lipophilicityto the compound and accordingly will have different behavior.

As used herein, the term “heteroalkyl” includes a chain of atoms thatincludes both carbon and at least one heteroatom, and is optionallybranched. Illustrative heteroatoms include nitrogen, oxygen, and sulfur.In certain variations, illustrative heteroatoms also include phosphorus,and selenium. As used herein, the term “cycloheteroalkyl” includingheterocyclyl and heterocycle, includes a chain of atoms that includesboth carbon and at least one heteroatom, such as heteroalkyl, and isoptionally branched, where at least a portion of the chain is cyclic.Illustrative heteroatoms include nitrogen, oxygen, and sulfur. Incertain variations, illustrative heteroatoms also include phosphorus,and selenium. Illustrative cycloheteroalkyl include, but are not limitedto, tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl,morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl, and the like.

The term “optionally substituted” as used herein includes thereplacement of hydrogen atoms with other functional groups on theradical that is optionally substituted. Such other functional groupsillustratively include, but are not limited to, amino, hydroxyl, halo,thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl,nitro, sulfonic acids and derivatives thereof, carboxylic acids andderivatives thereof, and the like. Illustratively, any of amino,hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl,arylheteroalkyl, and/or sulfonic acid is optionally substituted.

In illustrative embodiments, the nucleophile is a diamine, triamine,tetraamine, or pentamine. In one embodiment, the polyamine is a triamineselected a diethylenetriamine, 1-piperazineethaneamine, orbis(hexamethylene)triamine. In another embodiment, the polyamine is atetramine, for example triethylenetetramine. In another embodiment, thepolyamine is a pentamine, for example tetraethylenepentamine.

One aspect of the nucleophile is that it may possess low sterichindrance. For example, Q is selected such that the nucleophile has lowsteric hindrance. For example, if Q is essentially linear and has alength of at least three atoms, the nucleophilic moiety and thestabilizing moiety are sufficiently spaced so that the nucleophile isable to react with the electrophile.

While not being limited to a particular theory, the stabilization moietyis so-called because it may stabilize a reaction intermediate asdescribed herein. However, in another aspect of the present disclosure,the stabilization moiety may also serve as a reactant within the scopeof the present disclosure. As such, rearrangement products existingafter the reaction between the nucleophilic moiety and the carbohydratemay convert or return the stabilization moiety into a group that reactsor is capable of reacting with another carbohydrate. Accordingly, thestabilization moiety may convert or return to the form of a nucleophilicmoiety and react with the carbohydrate accordingly.

In illustrative embodiments, the Q group, as described herein, can serveto isolate the two groups such that R₁ and R₂ are essentially unaffectedby the chemistry occurring at the other position. As such, the Q groupmay or may not be serving in the capacity of a stabilization moiety.According to this theory, the advantages gained through utilization of adi-functional nucleophile are attributable primarily to the fact that asingle di-functional compound can form a cross-link between twocarbohydrate compounds. Because the two functional groups are linkedthrough a Q group, upon reaction of both R₁ and R₂, the result is ahigher molecular weight product than if R₁ and R₂ were not linkedthrough the Q group. As such, the R₁ and R₂ can be selected from thegroup consisting of an amine, an azide, a cyanate, an isocyanate, athiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl,a carboxylate, a hydroxyl, an alkoxide, an amide, an imine, an imide, anitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, ahydrogen, a sulphono, a sulpho, a sulfinyl, and a sulfhydryl (thiol).

In illustrative embodiments, the Q group is of the type which enablesthe chemical communication between R₁ and R₂. For example, Q may enablechemical communication by enabling resonance and polarity shifts from R₁to R₂. In other embodiments, Q may be of a length that reactions ateither R₁ and R₂ cause changes to the electron distribution at the othergroup (R₁ or R₂). In one embodiment, the nucleophile includes astabilization moiety and a nucleophilic moiety. In one embodiment, thenucleophilic moiety is selected from the group consisting of an amine,an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate,a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and analkoxide. In another embodiment, the cationic stabilization moiety isselected from the group consisting of an amine, an amide, an imine, animide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, ahydroxyl, a hydrogen, a sulphono, a sulpho, a sulfinyl, and a sulfhydryl(thiol).

In one embodiment, the nucleophile may include a polymeric polyamine.For example, polymeric polyamines within the scope of the presentdisclosure include chitosan, polylysine, polyethylenimine,poly(N-vinyl-N-methyl amine), polyaminostyrene and polyvinylamines. Inone embodiment, the polyamine comprises a polyvinyl amine. As usedherein, the polyvinyl amine can be a homopolymer or a copolymer.

While not limited to a particular theory, one aspect of the presentdisclosure is that the primary amine and the carbohydrate reactant areMaillard reactants that react to form a melanoidin product. FIG. 1 showsa schematic of a Maillard reaction, which culminates in the productionof melanoidins. In its initial phase, a Maillard reaction involves acarbohydrate reactant, for example, a reducing sugar (note that thecarbohydrate reactant may come from a substance capable of producing areducing sugar under Maillard reaction conditions). The reaction alsoinvolves condensing the carbohydrate reactant (e.g., reducing sugar)with an amine reactant, i.e., a compound possessing an amino group. Inother words, the carbohydrate reactant and the amine reactant are themelanoidin reactants for a Maillard reaction. The condensation of thesetwo constituents produces an N-substituted glycosylamine. For a moredetailed description of the Maillard reaction see, Hodge, J. E.Chemistry of Browning Reactions in Model Systems J. Agric. Food Chem.1953, 1, 928-943, the disclosure of which is hereby incorporated hereinby reference. The literature on Maillard reactions focuses on amelanoidins produced from amino acids. The present disclosure can bedistinguished from these references in that the nucleophiles within thescope of the present disclosure also include a stabilization moiety.Common amino acids which are considered within the scope of the presentdisclosure include asparagine, glutamine, histidine, lysine, andarginine.

Without being bound to theory, the covalent reaction between thenucleophile and the carbohydrate reactant will be described in greaterspecificity. As described herein, the pathway of the present reaction isdistinct from those taught in the prior art for the following reasons:(1) the present reaction may occur completely at basic pH, (2) thenucleophile is di-functional having a nucleophilic moiety and astabilization moiety, (3) the nucleophile, through its di-functionalityor another unrecognized phenomena, exhibits a lower activation energywithin the scope of the reaction which results in an unexpected increasein reaction rate and/or a decrease in the temperature at which thereaction will proceed.

In illustrative embodiments, the first step in the formation of highmolecular weight polymers from a nucleophile and a carbohydrate reactantis the condensation of the carbohydrate reactant and the nucleophile.Evidence indicates that the conditions described herein are especiallysuitable for driving this reaction to completion. First, it is believedthat the alkalinity of the binder solution drives the condensation. Forexample, it has been shown that sugars and nucleophiles such as aminesundergo browning in aqueous solution in proportion to the basic strengthof the amines employed or the pH of the solution. In this example, it isbelieved that the N-substituted glycosylamines remain undissociated inaqueous solutions to appreciable extents. Thus, the irreversibletransformations that the undissociated molecules undergo must beconsidered. While it is known that the condensation reaction isreversible, we discovered that this reaction can be further driven tocompletion, in accordance with Le Chatelier's principle by theconcurrent dehydration of the binder solution. As such, it wasestablished that initially a primary constituent of the uncured bindercomposition was the condensation products of the nucleophile and thecarbohydrate.

The second step in the conversion of the binder reactants to highmolecular weight polymer products may be a rearrangement. An exemplaryrearrangement is shown as a schematic of a Amadori rearrangement in FIG.2. Referring to FIG. 2, the N-glycosyl derivatives of the representativeamines are in equilibrium with the cation of a Schiff base. While thisequilibrium favors the N-glycosylamine, further rearrangement of thecation of a Schiff base to the enol or keto form is known to proceedspontaneously. It was discovered that this spontaneous reaction isfurther facilitated by dehydration, as the rate was increased indehydrated samples. One aspect of the present disclosure is that thestructure of a nucleophile specifically accelerates this rearrangementby stabilizing the positive charge that is acquired while the compoundis in the form of a cation of a Schiff base. It is believed that thisstabilization effect has not been discussed in the prior art or theliterature as the enhanced effect of using a nucleophile as such withinthe scope of the present disclosure has not previously been disclosed.Accordingly, one aspect of the present disclosure is that thenucleophile is of a type that provides stability to a cationic baseduring a rearrangement. In another aspect, the nucleophile is of a typethat provides stability to a cationic base during a rearrangement whilein a substantially dry state.

Another aspect of the present disclosure is that the carbohydratestructure is also believed to influence the kinetics of therearrangement. Specifically, it is known when the C-2 hydroxyl of acrystalline N-substituted glycosylamine was unsubstituted, the compoundwas slowly transformed during storage to the rearrangement product.However, if the C-2 hydroxyl was substituted, then the rearrangement wassubstantially inhibited. Accordingly, one aspect of the presentdisclosure is that a carbohydrate of the present disclosure isunsubstituted at the hydroxyl adjacent to the ketone or aldehyde.

In illustrative embodiments, the molar ratio of the carbohydratereactant to the nucleophile is in the range of about 1:1 to about 30:1.In another embodiment, the molar ratio of the carbohydrate reactant tothe nucleophile is in the range of about 2:1 to about 10:1. In yetanother embodiment, the molar ratio of the carbohydrate reactant to thenucleophile is in the range of about 3:1 to about 6:1. According to oneaspect, the cure rate is a function of the molar ratio of thecarbohydrate reactant to the primary polyamine. According to thisfunction, it was established that as the ratio decreased, the cure rateincreased; thus the cure time decreased. Accordingly, the one aspect ofthe present disclosure is that the cure time is directly related to themolar ratio of the carbohydrate reactant to the polyamine provided thatother parameters are held equivalent. In another aspect, the binder curetime is reduced to the cure time of a comparable phenol formaldehydebinder composition when the molar ratio of the carbohydrate reactant tothe nucleophile is equal to about 6:1. Accordingly, in one embodiment, abinder according to the present disclosure has a cure rate exceeding acomparable phenol formaldehyde binder system when the carbohydratereactant to nucleophile molar ratio is in the range of about 2:1 toabout 6:1.

Another aspect of the reaction, as described herein, is that initiallythe aqueous reactant solution (which may be dehydrated and used as abinder) has an alkaline pH. One aspect of the present disclosure is thatthe alkaline binder solution is less corrosive towards metal than acidicsolution. Accordingly, one feature of the present disclosure whichovercomes a substantial barrier to the industry is that the binderdescribed herein has low corrosivity towards the manufacturing equipmentwhich may be used to produce materials which include the present binderbecause of the alkaline binder composition. One distinguishing featureof the present disclosure over other recently described carbohydratebinder systems (e.g. U.S. Published Application No. 2007/0027283), isthat the reaction does not necessarily proceed through an acidicpathway. Rather, one aspect of the present disclosure is that theuncured binder may have an alkaline pH throughout the course of thechemical reaction which leads to the formation of the cured binder. Assuch, the uncured binder, throughout its use and storage does notpresent a corrosion risk. In illustrative embodiments, an aqueousextract of the cured binder has a pH in the range of about 5 to about 9.Furthermore, an aqueous extract of the polymeric product is essentiallycolorless.

In illustrative embodiments, a method of making a collection of matterbound with a polymeric binder comprises preparing a solution containingreactants for producing the polymeric binder and a solvent, wherein thereactants include a carbohydrate reactant and a nucleophile; disposingthe solution onto the collection of matter; volatilizing the solvent toform an uncured product, and subjecting the uncured product toconditions that cause the carbohydrate reactant and the nucleophile topolymerize to form the polymeric binder.

In illustrative embodiments, the collection of matter includesinsulating fibers. In one embodiment, a fiber insulation product isdescribed which includes insulating fibers and a binder. As used herein,the term “insulating fiber,” indicates heat-resistant fibers suitablefor withstanding elevated temperatures. Examples of such fibers include,but are not limited to, mineral fibers (glass fibers, slag wool fibers,and rock wool fibers), aramid fibers, ceramic fibers, metal fibers,carbon fibers, polyimide fibers, certain polyester fibers, and rayonfibers. Illustratively, such fibers are substantially unaffected byexposure to temperatures above about 120° C. In one embodiment, theinsulating fibers are glass fibers. In yet another embodiment, themineral fibers are present in the range from about 70% to about 99% byweight.

In illustrative embodiments, the collection of matter includescellulosic fibers. For example, the cellulosic fibers may be woodshavings, sawdust, wood pulp, or ground wood. In yet another embodiment,the cellulosic fibers may be other natural fibers such as jute, flax,hemp, and straw. The binder disclosed herein may be used as in the placeof the binder described in Published PCT application WO 2008/089847,which is incorporated herein by reference in its entirety. In oneembodiment, a composite wood board comprising wood particles and abinder is disclosed. In another embodiment, the composite wood board isformaldehyde free. In one embodiment, the composite wood board has anominal thickness range of greater than 6 mm to 13 mm, and has a modulusof elasticity (MOE) of at least about 1050 N/mm², a bending strength(MOR) of at least about 7 N/mm², and an internal bond strength (IB) ofat least 0.20 N/mm². In another embodiment, the composite wood board hasa nominal thickness range of greater than 6 mm to 13 mm, and has abending strength (MOR) of at least about 12.5 N/mm², and an internalbond strength (IB) of at least 0.28 N/mm². In another embodiment, thecomposite wood board has a nominal thickness range of greater than 6 mmto 13 mm, and has a modulus of elasticity (MOE) of at least about 1800N/mm², a bending strength (MOR) of at least about 13 N/mm², and aninternal bond strength (IB) of at least 0.40 N/mm². In anotherembodiment, the composite wood board has a modulus of elasticity (MOE)of at least about 1800 N/mm². In another embodiment, the composite woodboard has a modulus of elasticity (MOE) of at least about 2500 N/mm². Inanother embodiment, the composite wood board has a bending strength(MOR) of at least about 14 N/mm². In yet another embodiment, thecomposite wood board has a bending strength (MOR) is at least about 18N/mm². In one embodiment, the composite wood board has an internal bondstrength (IB) of at least 0.28 N/mm². In yet another embodiment, thecomposite wood board has an internal bond strength (IB) is at least 0.4N/mm². In yet another embodiment, the composite wood board swells lessthan or equal to about 12%, as measured by a change in thickness, after24 hours in water at 20° C. In another embodiment, the composite woodboard has a water absorption after 24 hours in water at 20° C. of lessthan or equal to about 40%.

In illustrative embodiments the composite wood board is a woodparticleboard, an orientated strandboard, or a medium densityfiberboard. In one embodiment, the binder comprises from about 8% toabout 18% by weight (weight of dry resin to weight of dry woodparticles) of the composite wood board. In another embodiment, thecomposite wood board further comprises a wax. In yet another embodiment,the composite wood board comprises from about 0.1% to about 2% wax byweight of the composite wood board. In illustrative embodiments, themethod of making a collection of matter bound with a polymeric bindermay further include preparing a solution by adding an amount of acarbohydrate reactant and an amount of a nucleophile so a molar ratio isin the range of about 2:1 to about 10:1. In one embodiment, preparingthe solution includes adding the carbohydrate reactant and the polyamineto an aqueous solution. In another embodiment, preparing the solutionincludes adjusting the pH of the solution to within the range of about 8to about 12. In yet another embodiment, the method of making acollection of matter bound with a polymeric binder may further comprisepackaging the uncured product in a packaging material suitable forstorage.

In illustrative embodiments, the present disclosure relates to acomposition comprising a collection of matter and a binder, the bindercomprising polymeric products of a reaction between a carbohydratereactant and a nucleophile, the polymeric products being substantiallywater insoluble. In one embodiment, the collection of matter includesmineral fibers, aramid fibers, ceramic fibers, metal fibers, carbonfibers, polyimide fibers, polyester fibers, rayon fibers, or cellulosicfibers. For example, cellulosic fibers may include wood shavings,sawdust, wood pulp, and/or ground wood. In one embodiment, thecollection of matter includes sand or other inorganic particulatematter. In one embodiment, the collection of matter is coalparticulates. In one embodiment, the carbohydrate reactant is selectedfrom the group consisting of dextrose, xylose, fructose,dihydroxyacetone, and mixtures thereof. In one embodiment, thenucleophile is R₁-Q-R₂, wherein Q is alkyl, cycloalkyl, heteroalkyl, orcycloheteroalkyl, each of which is optionally substituted, R₁ is anucleophilic moiety, and R₂ is a stabilization moiety.

In another embodiment, the composition further comprises asilicon-containing compound. In one embodiment the silicon-containingcompound is a functionalized silylether or a functionalizedalkylsilylether, such as for example, an amino-functionalizedalkylsilylether. For example, in one embodiment, the silicon-containingcompound may be gamma-aminopropyltriethoxysilane,gamma-glycidoxypropyltrimethoxysilane, oraminoethylaminopropyltrimethoxysilane, or a mixture thereof. In anotherembodiment, the silicon-containing compound may be an aminofunctionaloligomeric siloxane. In another embodiment, the composition comprises acorrosion inhibitor selected from the group consisting of dedusting oil,monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin(II)oxalate, and a methylhydrogen silicone fluid emulsion.

In further illustrative embodiments, the binder may be disposed upon acollection of fibers, substantially dehydrated, packaged, and thenstored or sold to another party. An uncured product sold to anotherparty for use in further manufacturing processes may be referred to as“ship-out uncured.” An uncured product stored for use in furthermanufacturing processes may be referred to as “plant uncured.” Inselling or storing this type of product, it is packaged in suitablecontainers or bags.

In illustrative embodiments, a packaged uncured fiber product comprisesan uncured binder composition and a collection of fibers, wherein (i)the uncured binder composition is in contact with the collection offibers consolidating the collection of fibers and (ii) the uncuredbinder composition in contact with the collection of fibers is packagedin a suitable packaging material. In one embodiment, the amount ofmoisture in the uncured binder composition may be in a range from about1% to about 15% by weight based on a total weight of the product. In yetanother embodiment, the suitable packaging material may be capable ofmaintaining the amount of moisture in the uncured binder composition towithin about 20% of an original moisture level for a period of one weekat an ambient temperature and an ambient pressure. In one embodiment,the packaged uncured fiber product comprises from about 3% to about 30%by weight of the uncured binder composition based on weight of thepackaged uncured fiber product without considering the weight of thesuitable packaging material. In one embodiment, the packaged uncuredfiber product comprises from about 60 to about 97% by weight fibersbased on weight of the packaged uncured fiber insulation product withoutconsidering the weight of the suitable packaging material.

One aspect of the present disclosure is that the binder described hereinis unexpectedly useful in applications ship-out uncured and plantuncured applications. Specifically, ship-out uncured products and plantuncured products are provided with an uncured binder so that the curingcan occur at a later time and in a later place. In the case of ship-outuncured, the curing temperature and time are properties of the productwhich are of great importance to the customers. Specifically, the curetemperatures must be sufficiently low such that the product can be curedusing their existing equipment. Furthermore, the cure time must besufficiently short such that the cycle time for curing the productsremains low. Within this industry, the manufacturing equipment andacceptable cycle times have been established for uncured productscomprising phenol formaldehyde type resins. Therefore, sufficiently lowcure temperatures are those cure temperatures suitable for curing acomparable phenol formaldehyde type product. Similarly, sufficiently lowcycle times are those cycle times which would be routine for curing acomparable phenol formaldehyde type product. One of ordinary skill inthe art will appreciate that neither cure time nor cure temperature canbe set forth as definite quantities because the specific applicationsmay have dramatically different parameters. However, it is wellunderstood that the cure time and cure temperatures of a model systemprovide sufficient representative information regarding the kinetics ofthe underlying chemical curing reaction so that reliable predictions ofbinder performance in the various applications can be made.

In illustrative embodiments, the cure time and the cure temperature ofthe binder is equal to or less than a comparable phenol formaldehydebinder composition. In one embodiment, the cure time of the binder isless than the cure time of a comparable phenol formaldehyde bindercomposition. In another embodiment, the cure temperature of the binderis less than the cure temperature of a comparable phenol formaldehydebinder composition. As used herein, a comparable phenol formaldehydebinder composition is like that described according to U.S. Pat. No.6,638,882, which patent is hereby incorporated by reference herein inits entirety.

As discussed below, various additives can be incorporated into thebinder composition. These additives give the binders of the presentinvention additional desirable characteristics. For example, the bindermay include a silicon-containing coupling agent. Many silicon-containingcoupling agents are commercially available from the Dow-CorningCorporation, Evonik Industries, and Momentive Performance Materials.Illustratively, the silicon-containing coupling agent includes compoundssuch as silylethers and alkylsilyl ethers, each of which may beoptionally substituted, such as with halogen, alkoxy, amino, and thelike. In one variation, the silicon-containing compound is anamino-substituted silane, such as, gamma-aminopropyltriethoxy silane(SILQUEST A-1101; Momentive Performance Materials, CorporateHeadquarters: 22 Corporate Woods Boulevard, Albany, N.Y. 12211 USA). Inanother variation, the silicon-containing compound is anamino-substituted silane, for example, aminoethylaminopropyltrimethoxysilane (Dow Z-6020; Dow Chemical, Midland, Mich.; USA). In anothervariation, the silicon-containing compound isgamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive). Inyet another variation, the silicon-containing compound is anaminofunctional oligomeric siloxane (HYDROSIL 2627, Evonik Industries,379 Interpace Pkwy, Parsippany, N.J. 07054).

The silicon-containing coupling agents are typically present in thebinder in the range from about 0.1 percent to about 1 percent by weightbased upon the dissolved binder solids (i.e., about 0.05% to about 3%based upon the weight of the solids added to the aqueous solution). Inone application, one or more of these silicon-containing compounds canbe added to the aqueous binder solution. The binder is then applied tothe material to be bound. Thereafter, the binder may be cured ifdesired. These silicone containing compounds enhance the ability of thebinder to adhere to the matter the binder is disposed on, such as glassfibers. Enhancing the binder's ability to adhere to the matter improves,for example, its ability to produce or promote cohesion in non- orloosely-assembled substance(s).

In another illustrative embodiment, a binder of the present inventionmay include one or more corrosion inhibitors. These corrosion inhibitorsprevent or inhibit the eating or wearing away of a substance, such as,metal caused by chemical decomposition brought about by an acid. When acorrosion inhibitor is included in a binder of the present invention,the binder's corrosivity is decreased as compared to the corrosivity ofthe binder without the inhibitor present. In one embodiment, thesecorrosion inhibitors can be utilized to decrease the corrosivity of theglass fiber-containing compositions described herein. Illustratively,corrosion inhibitors include one or more of the following, a dedustingoil, or a monoammonium phosphate, sodium metasilicate pentahydrate,melamine, tin(II) oxalate, and/or methylhydrogen silicone fluidemulsion. When included in a binder of the present invention, corrosioninhibitors are typically present in the binder in the range from about0.5 percent to about 2 percent by weight based upon the dissolved bindersolids. One aspect of the present disclosure is that the need forcorrosion inhibiting additives is greatly reduced by the alkalinity ofthe binder solution and the substantially dehydrated uncured binder. Inone embodiment, the binder is free from corrosion inhibitors and thecorrosivity of the binder solution is within the acceptable range.

In illustrative embodiments, the binder may further include anon-aqueous moisturizer. The non-aqueous moisturizer may include one ormore polyethers. For example, the non-aqueous moisturizer may include anethylene oxide or propylene oxide condensates having straight and/orbranched chain alkyl and alkaryl groups. In one embodiment, thenon-aqueous moisturizer includes a polyethylene glycol, a polypropyleneglycol ether, a thioether, a polyoxyalkylene glycol (e.g., JeffoxTP400®), a dipropylene glycol, and/or a polypropylene glycol (e.g.,Pluriol P425® or Pluriol 2000®). In one embodiment, the non-aqueousmoisturizer comprises a polyoxyalkylene glycol or a polypropyleneglycol. In another embodiment, the non-aqueous moisturizer includes acompound based on a polyhydroxy compound (e.g., a partially or fullyesterified polyhydroxy compound). In another embodiment, the non-aqueousmoisturizer includes a polyhydroxy based on a glycerine, a propyleneglycol, an ethylene glycol, a glycerine acetate, a sorbitol, a xylitolor a maltitol.

In another embodiment, the non-aqueous moisturizer includes othercompounds having multiple hydroxyl groups based on tetrahydrofuran, acaprolactone, and/or alkylphenoxypoly(ethyleneoxy)ethanols having alkylgroups containing from about 7 to about 18 carbon atoms and having fromabout 4 to about 240 ethyleneoxy units. For example, the non-aqueousmoisturizer may include a heptylphenoxypoly(ethyleneoxy)ethanol and/or anonylphenoxypoly(ethyleneoxy)ethanol. In another embodiment, thenon-aqueous moisturizer includes a polyoxyalkylene derivative of hexitolsuch as a sorbitan, sorbide, mannitan, and/or a mannide. In yet anotherembodiment, the non-aqueous moisturizer may include a partial long-chainfatty acids ester, such as a polyoxyalkylene derivative of sorbitanmonolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitantristearate, sorbitan monooleate, and/or sorbitan trioleate.

In illustrative embodiments, the non-aqueous moisturizer includes acondensate of ethylene oxide with a hydrophobic base, the base beingformed by condensing propylene oxide with propylene glycol. In oneembodiment, the non-aqueous moisturizer includes a sulfur containingcondensate, such as those prepared by condensing ethylene oxide with ahigher alkyl mercaptan (e.g., nonyl, dodecyl, tetradecyl mercaptan, oralkylthiophenols having about 6 to about 15 carbon atoms in the alkylgroup). In another embodiment, the non-aqueous moisturizer includes anethylene oxide derivative of a long-chain carboxylic acid, such aslauric, myristic, palmitic, or oleic acid. In yet another embodiment,the non-aqueous moisturizer includes an ethylene oxide derivative of along-chain alcohol such as octyl, decyl, lauryl, or cetyl alcohol. Inanother embodiment, the non-aqueous moisturizer includes an ethyleneoxide/tetrahydrofuran copolymer or an ethylene oxide/propylene oxidecopolymer.

The following examples illustrate specific embodiments in furtherdetail. These examples are provided for illustrative purposes only andshould not be construed as limiting the invention or the inventiveconcept to any particular physical configuration in any way.

EXAMPLES Example 1

A solution of 50 g dextrose (0.278 mol), 50 g hexamethylenediamine(0.431 mol) dissolved in 566.6 g deionized water (15% solids solution,pH 11.9) was heated to the boiling point of the solution. A brownishwater insoluble polymer was observed as a precipitate in the reactionvessel.

Example 2

From the above solution of 50 g dextrose (0.278 mol), 50 ghexamethylenediamine (0.431 mol) dissolved in 566.6 g deionized water(15% solids solution, pH 11.9), 2 g of the binder solution was appliedon a filter pad which is placed in a Moisture Balance and heated for 15min at 120° C. A brownish water insoluble polymer formed on the filterpad. An extraction of the cured filter pad using 100 g of deionizedwater is essentially colorless and has a pH of 6.8.

Example 3

A solution of 85 g dextrose (0.472 mol), 15 g hexamethylenediamine(0.129 mol) dissolved in 566.6 g deionized water (15% solids solution,pH 10.8) was prepared. 2 g of the binder solution was applied on afilter pad which is placed in a Moisture Balance and heated for 15 minat 140° C. A brownish water insoluble polymer formed on the filter pad.An extraction of the cured filter pad using 100 g of deionized water isessentially colorless and has a pH of 6.8.

Example 4

A solution of 95 g dextrose (0.528 mol), 5 g hexamethylenediamine (0.043mol) dissolved in 566.6 g deionized water (15% solids solution) wasprepared. 2 g of the binder solution was applied on a filter pad whichis placed in a Moisture Balance and heated for 15 min at 180° C. Abrownish water insoluble polymer formed on the filter pad. An extractionof the cured filter pad using 100 g of deionized water is essentiallycolorless and has a pH of 6.8.

Comparative Example 1

A solution of 180 g dextrose (1 mol) dissolved in 1020 g deionized water(15% solids solution) was prepared. 2 g of the binder solution wasapplied on a filter pad which is placed in a Moisture Balance and heatedfor 15 min at 180° C. A water insoluble polymer was not formed on thefilter pad. The resulting heat treated binder was essentially fullywater soluble.

Cure Rate and Cure Time:

Square Fiberglass mats (13″×13″) with a weight of 44 g (corresponding to34.5 g/ft²) were impregnated with a binder containing 15% solids. Excessof binder is removed by vacuum suction, and the moist mat is dried forat least 12 hours at 90° F. in an oven (recirculation).

The dried mat is cut in four squares of the same dimension. The squaresare stacked on top of each other, and at least one thermocoupleconnected to a recorder (i.e. oven mole) is placed in the middle of thestack between the 2^(nd) and 3^(rd) layer.

A mold press with temperature controlled platen is heated to 400° F.(204° C.). The sample with the prepared thermocouple is placed in themiddle of the platen, and pressed to a thickness of ⅝″ for a predefinedtime (i.e. 3.5 min, 4.0 min, 5.0 min, 6.0 min, 15 min).

Each molded sample was evaluated for the degree of cure by testingevenness of the surfaces, water hold-up, and extract. A sample wasdeemed to be cured when the surfaces are smooth without any “bumps”, thesample does not noticeably weaken when immersed in water, and nosignificant extract color is formed when immersing the sample in water.The temperature profile of the center of the sample is measured duringthe molding cycle and is shown in FIG. 3.

Comparative Example 2

Phenol Formaldehyde Binder.

Composition based on dry solids:

-   -   2.41 parts Ammonium Sulfate    -   1.08 part of Ammonia    -   0.21 parts Silane A1101    -   96.3% phenol formaldehyde-Resin:Urea Premix (70:30)        Comparative Example 2 is referred to as Binder 1 within FIG. 3.

Comparative Example 3

Carbohydrate-Inorganic Acid Binder.

Composition based on dry solids:

-   -   81.59 parts Dextrose    -   17.09 parts Ammonium Sulfate    -   1 part of Ammonia    -   0.3 parts Silane A1101        Comparative Example 3 is referred to as Binder 2 within FIG. 3.

Example 5

Composition based on dry solids:

-   -   80.94 parts Dextrose and Ammonia solution (an aqueous solution        containing 2 mol/liter Dextrose and 2 mol/liter Ammonia)    -   19.06 parts Hexamethylenediamine        Example 5 is referred to as Binder 4 within FIG. 3.

It was determined that the time required to achieve full cure of abinder within the scope of the present disclosure is less than that of 3comparative example binder systems having diverse chemistries. Thismodel system illustrates that the cure time, providing that othervariables are kept constant, is dependent on the chemistry of the bindersystem. The chemistry of an illustrative binder composition within thescope of the present disclosure achieves improved cure times incomparison to these other exemplary systems. The results are shownfollowing:

Binder Molding Time to achieve full cure Comparative Ex. 2—Binder 1Minimum of 240 seconds Comparative Ex. 3—Binder 2 Minimum of 300 secondsEx. 5—Binder 4 Cured at 210 seconds

Referring now to FIG. 3, shown is the temperature profile characteristicfor each of binders 1, 2, and 4. It was noted that the temperatureprofile is characteristic for each binder. It was not established thatthe cure rate and cure time is not characteristic of the curetemperature profile. However, the cure temperature profile helps tounderstand and predict cure rate and cure time. Specifically,Comparative Example 3 required the greatest cure time and similarly thecure temperature profile required the greatest amount of time toasymptotically maximize. Similarly, Example 5 required the least amountof time to asymptotically maximize and demonstrated the shortest curetime.

Carbohydrate Reactant: Polyamine Ratio Effect on Cure Cycle Time.

Wet Laid Mats (WLM) were made with varying ratios of dextrosemonohydrate (DMH) to Hexamethylenediamine (HMDA). The weight ratiostested include 75/25, 85/15, and 92/8 respectively.

A 15% Dextrose-HMDA Binder was applied to 5 WLM's. The following bindercompositions were prepared:

Example 6 Example 7 Example 8 DMH/HMDA 75/25 DMH/HMDA 85/15 DMH/HMDA92/8 Water 1677.45 g 1677.45 g 1677.45 g DMH 246.78 g 279.68 g 302.72 gHMDA 74.77 g 44.86 g 23.93 g Silane 1.00 g 1.00 g 1.00 g

The mats are prepared in 13″×13″ pieces, with a thickness of ⅜″. Thepress used to mold the mats is set at 400° F. Once the sample is moldedit is approximately ⅝″ thick. A temperature profile was first determinedin a 15 minute interval. The next sample was pressed for 4 minutes; thisis the time it takes to cure a comparable phenol formaldehyde bindercomposition (results not shown). The experiments were repeated withvarying cure times until the minimum time required to cure eachcomposition was determined. The extent to which each binder had curedwas determined based on weight. The following results were determined:

Cure Cycle Time Example 6 2:30 min. Example 7 4 min. Example 8 8 min.

As described above, comparable phenol formaldehyde based product (e.g.Comparative Example 2) cures with a 4 minute cycle time. Furthermore, acomparable carbohydrate based binder (e.g. Comparative Example 3) cureswith a 5 minute cycle time. These results indicate that a binder withinthe scope of the present disclosure with a carbohydrate reactant toprimary polyamine of 85/15 or lower cures at a comparable or faster ratethan the phenol formaldehyde based product. Further experiments showedthat the cure temperature can be lowered in products having a shortercure time to achieve equivalent cure times at lower temperatures. Theresults obtained agreed in principle to our expectations based on theArrhenius equation.

In addition to those examples described in detail, the followingexamples were made to ensure that the carbohydrate reactant andpolyamine may comprise a wide range of alternatives.

Carbohydrate Binder Ex. Polyamine Reactant Formed 9 hexamethylenediaminedextrose Yes 10 ethylenediamine dextrose Yes 11 diethylenetriaminedextrose Yes 12 hexamethylenediamine high fructose Yes corn syrup 13hexamethylenediamine sucrose Yes 14 octamethylenediamine dextrose Yes 15tetramethylenediamine dextrose Yes

Further Dextrose—Nucleophile Examples Example 16

A suspension of 56.08 g deionized water, 7.15 g dextrose monohydrate,and 3.5 g 1,12-diaminododecane was acidified with 11 N HCl to pH 1.0,and heated to 70° C. under agitation resulting into a clear, colorlesssolution. The solution forms a thermoset, water insoluble polymer at160° C. (Test condition: 2 g binder solution is applied on a filter padwhich is placed in a Moisture Balance. The filter pad is heated for 15min at 160° C.) An extract of the cured filter pad with 100 g ofdeionized water is essentially colorless.

Example 17

A solution of 8.25 g dextrose monohydrate, and 2.50 g1,5-diamino-2-methylpentane (Dytek A, Invista) dissolved in 56.08 gdeionized water forms a thermoset, water insoluble polymer at 160° C.(Test condition: 2 g binder solution is applied on a filter pad which isplaced in a Moisture Balance. The filter pad is heated for 15 min at160° C.) An extract of the cured filter pad with 100 g of deionizedwater is essentially colorless.

Example 18

A solution of 8.03 g dextrose monohydrate, and 2.70 gN-(3-aminopropyl)-1,3-propanediamine dissolved in 56.08 g deionizedwater forms a thermoset, water insoluble polymer at 200° C. (Testcondition: 2 g binder solution is applied on a filter pad which isplaced in a Moisture Balance. The filter pad is heated for 15 min at200° C.) An extract of the cured filter pad with 100 g of deionizedwater has a slight yellowish color.

Example 19

A solution of 3 g dextrose (0.016 mol) and 0.5 g hexamethylenediamine(0.004 mol) dissolved in 9 mL deionized water was prepared. Thisreaction mixture was heated at 100° C. for 1 hour before 0.7 g ofdithiothreitol (0.004 mol) was added to the mixture which was dropped ona filter pad, this filter pad was heated at 125° C. A brownish waterinsoluble polymer was formed on the filter pad.

Example 20

A solution of 3 g dextrose (0.016 mol), 0.5 g hexamethylenediamine(0.004 mol) dissolved in 9 mL deionized water was prepared. Thisreaction mixture was heated at 100° C. for 1 hour before 0.52 g ofbutanedithiol (0.004 mol) was added to the mixture which was dropped ona filter pad, this filter pad was heated at 125° C. A brownish waterinsoluble polymer was formed on the filter pad.

Procedure for Analyzing a Binder Sample with Gas Pyrolysis.

Approximately 10 g of a cured product having the binder thereon isplaced in a test tube, which tube is then heated to 1000° F. for 2.5minutes at which time the headspace is sampled and analyzed by gaschromatography/mass spectrometry (GC/MS) under the following conditions:Oven, 50° C. for one minute—10° C./minute to 300° C. for 10 minutes;Inlet, 280° C. splitless; Column, HP-5 30 mm×0.32 mm×0.25 um; Columnflow, 1.11 mL/minute Helium; Detector, MSD 280° C.; Injection volume, 1mL; Detector mode, scan 34-700 amu; Threshold, 50; and Sampling Rate, 22scans/second. A computer search of the mass spectrum of achromatographic peak in the sample is made against the Wiley library ofmass spectra. The best match is reported. A quality index (closeness ofmatch to the library spectra) ranging from 0 to 99 is generated. Onlythe identity of peaks with a quality index of greater than or equal to90 is reported.

The following table provides representative pyrolysis data that oneexpects from the GC/MS analysis of gaseous compounds produced duringpyrolysis of a melanoidin based binder composition.

Retention Time (min) Tentative Identification % Peak Area 1.152-cyclopenten-1-one 10.67 1.34 2,5-dimethyl-furan 5.84 3.54 furan 2.153.60 3-methyl-2,5-furandione 3.93 4.07 phenol 0.38 4.892,3-dimethyl-2-cyclopenten-1-one 1.24 5.11 2-methyl phenol 1.19 5.424-methyl phenol 2.17 6.46 2,4-dimethyl-phenol 1.13 10.57dimethylphthalate 0.97 17.89 octadecanoic acid 1.00 22.75 erucylamide9.72

Following is a listing of the species observed in the pyrolysis gaschromatography mass spectrometry (Py GC-MS) of a binder sample preparedusing hexamethylenediamine as the polyamine component. The pyrolysis wascarried out at 200° C., 300° C., and 770° C. Fingerprinting shows a verysignificant peak which corresponds to acetic acic in the masschromatogram at both 200° C. and 300° C., which was not seen in a samplemade using dextrose and ammonium sulfate (see Comparative Example 3), inwhich the significant volatile was SO₂, particularly at 300° C. At 770°C., the peaks observed, in order of increasing retention time wereassigned as follows: A: Co-eluting C₅H₁₀, C₅H₁₂, acetone, possibly lowmw acetic acid ester; B: C₅H₈ diene; C: C₅H₈ diene; D: likely apentanol; E: C₆H₁₂−a methyl pentene; F: hexane; G: methylcyclopentane;H: a cyclohexadiene; I: C₆H₁₀−probably a methylcyclopentane; J: benzene;K: acetic acid; L: cyclohexene; M: probably nonanol; N:2-methyl-3-pentanone; O: 2,5-dimethylfuran; P: C₇H₁₀+unassignedco-elute; Q: pyridine+unassigned co-elute; R: toluene; S: possiblydecenal+unassigned co-elute; T: 2-ethyl-5-methylfuran; U: amethylpyridine; V: a methylpyrrole; W: a xylene; X: unassigned−withalcohol functionality; Y: unassigned; Z: a xylene+unassigned co-elute;AA: unassigned; AB: a dimethylpyrrole; AC: a dimethylpyridine; AD: adimethylpyridine; AE: unassigned; AF: unassigned; AG: an ethylmethylpyrrole+unassigned co-elute; AI: an unassigned but distinct massspectrum (N-containing), pyrrole related; AJ: an unassigned but distinctmass spectrum (N-containing), possibly an acetamide; AK: an unassignedbut distinct mass spectrum (N-containing), pyrrole related; AL: anunassigned but distinct mass spectrum (N-containing), pyrrole related;AM: an unassigned but distinct mass spectrum (N-containing), pyrrolerelated. The distinct mass spectra seen from peaks AI to AM are not seenin the data of prior binders not having the polyamine component.

Procedure for Evaluating Dry and Weathered Tensile Strength.

When evaluated for their dry and “weathered” tensile strength, glassbead-containing shell bone compositions prepared with a given binderprovide an indication of the likely tensile strength and the likelydurability, respectively, of a fiberglass product prepared with thatparticular binder. Predicted durability is based on a shell bone'sweathered tensile strength: dry tensile strength ratio. Shell bones areprepared, weathered, and tested as follows, for example, for ahexamethylenediamine-dextrose binder mixture.

A shell bone mold (Dietert Foundry Testing Equipment; Heated ShellCuring Accessory, Model 366, and Shell Mold Accessory) is set to adesired temperature, generally 425° F., and allowed to heat up for atleast one hour. While the shell bone mold is heating, approximately 100g of an aqueous binder (generally 15% in binder solids) is prepared(e.g. as described in Example 7). Using a large glass beaker, 727.5 g ofglass beads (Quality Ballotini Impact Beads, Spec. AD, US Sieve 70-140,106-212 micron-#7, from Potters Industries, Inc.) are weighed bydifference. The glass beads are poured into a clean and dry mixing bowl,which bowl was mounted onto an electric mixer stand. Approximately 75 gof aqueous binder is poured slowly into the glass beads in the mixingbowl. The electric mixer is then turned on and the glass beads/bindermixture is agitated for one minute. Using a large spatula, the sides ofthe whisk (mixer) are scraped to remove any clumps of binder, while alsoscraping the edges wherein the glass beads lay in the bottom of thebowl. The mixer is then turned back on for an additional minute, andthen the whisk (mixer) is removed from the unit, followed by removal ofthe mixing bowl containing the glass beads/binder mixture. Using a largespatula, as much of the binder and glass beads attached to the whisk(mixer) as possible are removed and then stirred into the glassbeads/binder mixture in the mixing bowl. The sides of the bowl are thenscraped to mix in any excess binder that might have accumulated on thesides. At this point, the glass beads/hexamethylenediamine-dextrosebinder mixture is ready for molding in a shell bone mold.

The slides of the shell bone mold are confirmed to be aligned within thebottom mold platen. Using a large spatula, a glassbeads/hexamethylenediamine-dextrose binder mixture is then quickly addedinto the three mold cavities within the shell bone mold. The surface ofthe mixture in each cavity is flattened out, while scraping off theexcess mixture to give a uniform surface area to the shell bone. Anyinconsistencies or gaps that existed in any of the cavities are filledin with additional glass beads/hexamethylenediamine-dextrose bindermixture and then flattened out. Once a glassbeads/hexamethylenediamine-dextrose binder mixture is placed into theshell bone cavities, and the mixture is exposed to heat, curing begins.As manipulation time can affect test results, e.g., shell bones with twodifferentially cured layers can be produced; shell bones are preparedconsistently and rapidly. With the shell bone mold filled, the topplaten is quickly placed onto the bottom platen. At the same time, orquickly thereafter, measurement of curing time is initiated by means ofa stopwatch, during which curing the temperature of the bottom platenranged from about 400° F. to about 430° F., while the temperature of thetop platen ranged from about 440° F. to about 470° F. At seven minuteselapsed time, the top platen is removed and the slides pulled out sothat all three shell bones can be removed. The freshly made shell bonesare then placed on a wire rack, adjacent to the shell bone mold platen,and allowed to cool to room temperature. Thereafter, each shell bone islabeled and placed individually in a plastic storage bag labeledappropriately. If shell bones can not be tested on the day they wereprepared, the shell bone-containing plastic bags were placed in adesiccator unit.

Conditioning (Weathering) Procedure for Shell Bones:

A Blue M humidity chamber is turned on and then set to provideweathering conditions of 90° F. and 90% relative humidity (i.e., 90°F./90% rH). The water tank on the side of the humidity chamber ischecked and filled regularly, usually each time it is turned on. Thehumidity chamber is allowed to reach the specified weathering conditionsover a period of at least 4 hours, with a day-long equilibration periodbeing typical. Shell bones to be weathered are loaded quickly (sincewhile the doors are open both the humidity and the temperaturedecrease), one at a time through the open humidity chamber doors, ontothe upper, slotted shelf of the humidity chamber. The time that theshell bones are placed in the humidity chamber is noted, and weatheringis conducted for a period of 24 hours. Thereafter, the humidity chamberdoors are opened and one set of shell bones at a time are quicklyremoved and placed individually into respective plastic storage bags,being sealed completely. Generally, one to four sets of shell bones at atime are weathered as described above. Weathered shell bones areimmediately taken to the Instron room and tested.

Test Procedure for Breaking Shell Bones:

In the Instron room, the shell bone test method is loaded on the 5500 RInstron machine while ensuring that the proper load cell is installed(i.e., Static Load Cell 5 kN), and the machine is allowed to warm up forfifteen minutes. During this period of time, shell bone testing gripsare verified as being installed on the machine. The load cell is zeroedand balanced, and then one set of shell bones is tested at a time asfollows: A shell bone is removed from its plastic storage bag and thenweighed. The weight (in grams) is then entered into the computerassociated with the Instron machine. The measured thickness of the shellbone (in inches) is then entered, as specimen thickness, three timesinto the computer associated with the Instron machine. A shell bonespecimen is then placed into the grips on the Instron machine, andtesting initiated via the keypad on the Instron machine. After removinga shell bone specimen, the measured breaking point is entered into thecomputer associated with the Instron machine, and testing continueduntil all shell bones in a set are tested.

Carbohydrate Reactant: Polyamine Ratio Effect on Shell Bone Properties.

Shell Bones were made with varying ratios of dextrose monohydrate (DMH)to Hexamethylenediamine (HMDA) with a silane additive (ISIO200) wereexamined as described above, at a test speed of 25 mm/min. The weightratios tested include 90/10, 85/15, 80/20 and 75/25, respectively.

Stress at peak/MNm⁻² Strength Dry Weathered Loss/% 90% DMH + 10% HMDA +0.3% 2.954 1.929 34.69 ISIO200, pH 11.06 85% DMH + 15% HMDA + 0.3% 2.5732.017 21.61 ISIO200, pH 11.29 80% DMH + 20% HMDA + 0.3% 2.747 2.34414.68 ISIO200, pH 11.54 75% DMH + 25% HMDA + 0.3% 2.735 2.073 24.21ISIO200, pH 11.71

Example Glass Wool (Fiber Glass) Trials

Comparisons of the qualities of two glucose-hexamethylenediamine binderswith a standard binder in terms of curing and rigidity on a glass woolproduct (Ac+032 100 mm 1200 mm width; 32 kg/m³-15 m/min) were carriedout by measuring the parting strength and density.

Binder 1: 85% glucose-15% hexamethylenediamine.

Binder 2: 90% glucose-10% hexamethylenediamine.

Ordinary Parting Strength (Before Autoclave) and Weathered PartingStrength (After Autoclave) may be measured as described in InternationalPatent Application, Publication Number WO 2008/089851 or WO2009/019235.

Parting Strength on a Standard Binder:

BEFORE AUTOCLAVE AFTER AUTOCLAVE Weight (g) Force (N) density (kg/m³)Weight (g) Force (N) density (kg/m³) 1 21.90 72.0 34.5 7 22.00 48.8 34.62 21.00 64.0 33.1 8 21.00 50.7 33.1 3 18.20 51.7 28.7 9 19.80 46.0 31.24 18.80 53.0 29.6 10 17.90 35.6 28.2 5 19.90 50.6 31.3 11 20.10 52.531.7 6 20.40 60.5 32.1 12 19.70 43.9 31.0 Total 120.20 351.8  31.6 Total120.50 277.5 31.6 35861.4 g 28287.5 g P.S. BEFORE: 298.3 gf/gwt P.S.AFTER: 234.8 gf/gwt LOSS: 63.6 gf/gwt ie 21.3%Parting Strength on Binder 1:

BEFORE AUTOCLAVE AFTER AUTOCLAVE Weight (g) Force (N) density (kg/m³)Weight (g) Force (N) density (kg/m³) 1 22.00 95.6 34.6 7 19.80 50.0 31.22 18.70 53.9 29.5 8 17.80 46.7 28.0 3 18.20 63.9 28.7 9 17.80 51.2 28.04 18.10 62.6 28.5 10 20.50 59.3 32.3 5 20.50 75.0 32.3 11 18.40 46.029.0 6 18.70 60.3 29.5 12 18.60 47.3 29.3 Total 116.20 411.3  30.5 Total112.90 300.5 29.6 41926.6 g 30632.0 g P.S. BEFORE: 360.8 gf/gwt P.S.AFTER: 271.3 gf/gwt LOSS: 89.5 gf/gwt ie 24.8%Parting Strength on Binder 2:

BEFORE AUTOCLAVE AFTER AUTOCLAVE Weight (g) Force (N) density (kg/m³)Weight (g) Force (N) density (kg/m³) 1 18.50 51.5 29.1 7 19.40 52.2 30.62 19.50 64.5 30.7 8 20.10 52.7 31.7 3 21.30 75.6 33.5 9 19.30 54.5 30.44 20.80 78.8 32.8 10 19.80 57.2 31.2 5 19.80 64.4 31.2 11 19.80 58.231.2 6 18.40 70.0 29.0 12 18.80 51.9 29.6 Total 118.30 404.8  31.1 Total117.20 326.7 30.8 41264.0 g 33302.8 g P.S. BEFORE: 348.8 gf/gwt P.S.AFTER: 284.2 gf/gwt LOSS: 78.1 gf/gwt ie 19.3%Observations during the trial: The product was browner on the line withthe two glucose-hexamethylenediamine binders.

Conclusions: With the two glucose-hexamethylenediamine binders, theparting strength (which is a longitudinal tensile strength) resultsshowed a significant improvement; and a significant improvement wasobserved in three other rigidity tests (“60°” test—sagging measured whenleaned at 60° against a chute; “table” test—sagging measured against ahorizontal plane; and Acermi test—sagging measured 35 cm from the edgeof a table).

Example Particle Board Trial

Comparisons of the qualities of particle boards made using aurea-formaldehyde binder (UF E0) and using a carbohydrate polyamine(hexamethylenediamine) binder were carried out under the followingconditions.

Board size: 350×333 mm and mainly 10 mm thick (2×20 mm)

Platen temperature: 195° C. mainly but also, 175 and ˜215° C.

Pressure: 3.5 Mpa (35 bar) Quoted—Actual 35 Kg/cm², 56 bar to achieve.

Density target: 650 kg/m³

Pre-form prepared prior to pressing.

Results:

PressTime IB Strength Binder (secs) (Mpa) UF E0 150 0.75 100 0.69 800.66 Carbohydrate 300 0.92 polyamine 240 0.99 180 0.88 150 0.73 120 0.6890 0.15All boards prepared appeared of high quality; no splits or degassingwere observed. The boards made with this carbohydrate polyamineformulation match urea formaldehyde board when they are cured for 150seconds.

The invention claimed is:
 1. A method of making a composite wood boardcomprising a collection of matter comprising cellulosic fibers boundwith a cured thermoset polymeric binder, the method comprising: (i)preparing an aqueous binder solution containing reactants for producingthe cured thermoset polymeric binder, wherein the reactants include areducing sugar and a nucleophile R₁-Q-R₂, wherein; Q is alkyl,cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which isoptionally substituted, R₁ is selected from the group consisting of anamine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, athiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, ahydroxyl, and an alkoxide, and R₂ is selected from the group consistingof an amine, an amide, an imine, an imide, a nitro, a nitrate, apyridine, a phosphate, a phosphono, a hydroxyl, a sulphono, a sulpho, asulfinyl, and a sulfhydryl, provided that when the nucleophile consistsof polyethylenimine, the mole ratio of the reducing sugar to thenucleophile is in the range of 1:1 to 30:1; (ii) disposing the aqueousbinder solution onto a collection of matter; (iii) drying the aqueousbinder solution to form an uncured product; and (iv) thermally curingthe uncured product which comprises 3% to 25% of dry binder solids(total uncured solids by weight) to form the composite wood board boundwith the cured thermoset polymeric binder.
 2. The method of claim 1,wherein preparing the aqueous binder solution includes at least one ofthe steps selected from the group consisting of: a) adding an amount ofthe reducing sugar and an amount of the nucleophile so a weight ratio ofthe reducing sugar to the nucleophile is in the range of about 2:1 toabout 10:1; b) adding the reducing sugar and the nucleophile to anaqueous solution; and c) adjusting the pH of the solution to within therange of about 8 to about
 12. 3. The method of claim 1, in which thecured thermoset polymeric binder is formaldehyde free.
 4. The method ofclaim 1, in which neither formaldehyde nor phenol is used as a reagent.5. The method of claim 1, wherein the cellulosic fibers comprises matterselected from the group consisting of wood shavings, sawdust, wood pulp,ground wood, jute, flax, hemp and straw.
 6. The method of claim 1,wherein the weight ratio of the reducing sugar to the nucleophile is inthe range of 2:1 to 10:1.
 7. The method of claim 1, wherein the reducingsugar is selected from the group consisting of dextrose, xylose,fructose, dihydroxyacetone, and mixtures thereof.
 8. The method of claim1, wherein R₁ and R₂ form covalent bonds with the reducing sugar to formthe polymeric binder.
 9. The method of claim 1, wherein R₁ is selectedfrom the group consisting of an azide, a cyanate, an isocyanate, athiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl,a carboxylate, a hydroxyl, and an alkoxide, and R₂ is selected from thegroup consisting of an amine, an amide, an imine, an imide, a nitro, anitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a sulphono, asulpho, a sulfinyl, and a sulfhydryl.
 10. The method of claim 1, whereinR₁ is selected from the group consisting of an amine, an azide, acyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen,a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and an alkoxide,and R₂ is a selected from the group consisting of an amide, an imine, animide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, ahydroxyl, a sulphono, a sulpho, a sulfinyl, and a sulfhydryl.
 11. Themethod of claim 1, wherein R₁ is selected from the group consisting ofan azide, a thiol, a halogen, a carboxyl, a carboxylate, a hydroxyl, andan alkoxide, and R₂ is a selected from the group consisting of an imine,a pyridine, a phosphate, a phosphono, a hydroxyl, a sulfinyl, and asulfhydryl.
 12. The method of claim 1, wherein R₁-Q-R₂ does not consistof polyethylenimine.
 13. The method of claim 1, wherein neither R₁ norR₂ is an amine.
 14. The method of claim 1, wherein R₁-Q-R₂ is a primaryamine having only one primary amine group.
 15. The method of claim 1,wherein Q is an alkyl selected from the group consisting of C₂-C₂₄. 16.The method of claim 1, wherein Q is an alkyl selected from the groupconsisting of C₂-C₈.
 17. The method of claim 1, wherein Q is an alkylselected from the group consisting of C₃-C₇.
 18. The method of claim 1,wherein Q is a C₆ alkyl.
 19. The method of claim 1, wherein Q is acycloalkyl selected from the group consisting of a cyclohexyl,cyclopentyl and cyclobutyl.
 20. The method of claim 1, wherein R₁-Q-R₂is 2-[(2-aminoethyl)amino]ethanol.
 21. The method of claim 1, whereineach of R₁ and R₂ is thiol.
 22. The method of claim 1, wherein R₁ is anamine and R₂ is an amine, an amide, an imine, or an imide.
 23. Themethod of claim 1, wherein R₁ is an amine and R₂ is an amine.
 24. Themethod of claim 1, wherein the mole ratio of the reducing sugar to thenucleophile is in the range of 1:1 to 30:1.
 25. The method of claim 1,wherein the mole ratio of the reducing sugar to the nucleophile is inthe range of 2:1 to 10:1.
 26. The method of claim 1, wherein the moleratio of the reducing sugar to nucleophile is in the range of 3:1 to6:1.
 27. The method of claim 1, wherein preparing the aqueous bindersolution includes adjusting the pH of the aqueous binder solution towithin the range of 8 to
 12. 28. The method of claim 1, wherein theaqueous binder solution has an alkaline pH.
 29. The method of claim 1,wherein the cured thermoset polymeric binder is water insoluble.
 30. Themethod of claim 1, wherein the cured thermoset polymeric binder stronglyabsorbs light at 420 nm.
 31. The method of claim 1, wherein the aqueousbinder solution is acid-free.
 32. The method of claim 1, wherein thecollection of matter and the cured thermoset polymeric binder furthercomprises a material selected from the group consisting of asilicon-containing compound, gamma-aminopropyltriethoxysilane,gamma-glycidoxypropyltrimethoxysilane,aminoethylaminopropyltrimethoxysilane, an aminofunctional oligomericsiloxane and mixtures thereof.
 33. The method of claim 1, wherein thecollection of matter and the cured thermoset polymeric binder furthercomprises a corrosion inhibitor selected from the group consisting ofdedusting oil, monoammonium phosphate, sodium metasilicate pentahydrate,melamine, tin (II)oxalate, and a methylhydrogen silicone fluid emulsion.34. The method of claim 1, wherein the binder further comprises anon-aqueous moisturizer.